EP1216134A1 - Air cooling systems for preform molding - Google Patents
Air cooling systems for preform moldingInfo
- Publication number
- EP1216134A1 EP1216134A1 EP00940096A EP00940096A EP1216134A1 EP 1216134 A1 EP1216134 A1 EP 1216134A1 EP 00940096 A EP00940096 A EP 00940096A EP 00940096 A EP00940096 A EP 00940096A EP 1216134 A1 EP1216134 A1 EP 1216134A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- air
- cooling
- preforms
- amplifier
- station
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/72—Heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/72—Heating or cooling
- B29C45/7207—Heating or cooling of the moulded articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/72—Heating or cooling
- B29C45/7207—Heating or cooling of the moulded articles
- B29C2045/7214—Preform carriers for cooling preforms
- B29C2045/7228—Preform carriers for cooling preforms turret-like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/081—Specified dimensions, e.g. values or ranges
- B29C2949/0811—Wall thickness
- B29C2949/0817—Wall thickness of the body
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
- B29C2949/0872—Weight
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/64—Heating or cooling preforms, parisons or blown articles
- B29C49/6409—Thermal conditioning of preforms
- B29C49/6427—Cooling of preforms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/64—Heating or cooling preforms, parisons or blown articles
- B29C49/6409—Thermal conditioning of preforms
- B29C49/6427—Cooling of preforms
- B29C49/6435—Cooling of preforms from the outside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
Definitions
- the present invention relates to an air cooling system to be used in connection with a preform molding machine which makes advantageous use of air amplifiers to cool the molded preforms and to a method of using same.
- Cooling preforms by means of blowing air on their surfaces after the preform has been removed from a mold is shown in Japanese patent publication 7-171888 to Sumitomo. Further, U.S. Patent No. 5,232,715 to Fukai teaches blowing air over the outside of a preform while it is held on a cooling mandrel. In both of these prior art examples, the preforms have been removed from the mold and are being cooled in a downstream piece of equipment. In order for the preforms to be removed from the mold without damage, sufficient cooling must take place in the mold to allow damage free ejection. Thus, a cycle time penalty has been accepted in order to do downstream cooling.
- U.S. Patent No. 4,449,913 to Krishnakumar shows blowing air over the outside of preforms while they are still on injection molding cores that are mounted on a turret block.
- the air blowing nozzles are at a fixed distance from the preforms.
- the Krishnakumar patent lacks any teaching of an air amplifier or how different cooling effects can be achieved at different areas of a preform surface.
- the present invention relates to an apparatus and a method of cooling molded preforms.
- the apparatus and method make advantageous use of air amplifiers to create a flow of cooling air over the molded preforms.
- the air amplifiers are mounted to a part removal and cooling robot.
- a plurality of air amplifier stations are positioned about an index block to cool the molded preforms.
- a vacuuming system is provided to improve the adherence of the air flow created by the air amplifiers to the exterior surfaces of the molded preforms.
- the air amplifiers are mounted to a movable plate and each amplifier has an internal bore sized to receive a molded preform to be cooled.
- the method of the present invention broadly comprises forming a plurality of molded preforms having neck, body and gate areas on a set of mold cores, moving the molded preforms to a position remote from a molding station, and blowing cooling air over exterior surfaces of the molded preforms while the molded preforms are positioned on the mold cores.
- the blowing step comprises generating a flow of cooling air using at least one air amplifier.
- FIG. 1 is a side view of a clamp portion of an index style injection molding machine with an air amplifier installation combined with a part removal robot;
- FIG. 2 is a schematic explanation of the operation of an air amplifier
- FIG. 3 is a schematic view of a preform
- FIG. 4a is a graphical representation of a thermal decay baseline data
- FIG. 4b is a graphical representation of thermal decay profile achieved using the apparatus of the present invention
- FIG. 5 is a side view of the clamp portion of an index style injection molding machine with multiple air amplifier installations
- FIG. 6 is a schematic view of air flow from an air amplifier in an embodiment in accordance with the present invention.
- FIG. 7 is a schematic view of an alternative embodiment of a preform cooling system in accordance with the present invention.
- FIG. 8 is a schematic view of another alternative embodiment of a preform cooling system in accordance with the present invention.
- FIG. 1 shows an index style clamp portion of an injection molding machine 10 used for molding tubular articles or preforms 12, such as PET preforms weighing 28 grams having an average wall thickness in the body portion of 4.00 mm and molded from 9921 grade polyethylene terephthalate material .
- the machine 10 is equipped with a 48 cavity hot runner mold 14 having four core sets 16, each mounted to one face 18 of a four faced index block 24.
- the mold 14 also includes a stationary mold half 20 which has a mold cavity half 22 which mates with one of the core sets 16 when the index block 24 has been moved into a mold closed position.
- molten plastic material to be molded is fed into the molds through the mold cavity half 22.
- the mechanism for introducing molten plastic material into the molds does not form part of the present invention and therefore has not been described in detail. Any suitable means known in the art for injecting plastic material into a mold may be utilized.
- the mechanism for moving the index block 24 between mold closed and mold open positions and for rotating the block 24 does not form part of the present invention. Therefore, the moving and rotating mechanism (s) has not been described in detail. Any suitable moving and rotating mechanism (s) known in the art may be utilized.
- each of the mold cores 16 may be cooled using any suitable cooling means known in the art.
- a first batch of the molded preforms face a part removal and cooling robot 28.
- the cycle time for each block rotation is approximately 15 seconds during which time the preforms 12 on the mold cores 16 facing the part removal and cooling robot 28 are subjected to supplementary cooling from ambient or chilled air blown over their outer surfaces.
- the preforms 12 are ejected from the mold cores 16 into the cooled part removal tubes 30 or 32 for additional cooling if necessary.
- Any suitable means known in the art may be used to eject the cooled preforms 12 from the mold cores 16. Since the ejection mechanism does not form part of the present invention, it has not been described in detail.
- the part removal and cooling robot 28 includes an air amplifier station 34 for cooling the preforms 12 while they are on the mold cores 16.
- a rotary head 26 moves either of the removal tube sets 30 and 32 or the air amplifier station 34 into alignment with the set of preforms 12 while they are on their respective mold cores 16.
- the part removal and cooling robot 28 is mounted on a movable carriage 36 connected by a continuous belt 38 to an electric linear drive 40 such that the movable carriage 36, and hence the robot 28, can be moved toward and away from the index block 24 so that the distance between either the air amplifier station 34 or either of the part removal tubes 30 or 32 and the corresponding preforms 12 can be varied.
- the air amplifier station 34 comprises a mounting plate 42 on which are mounted a plurality of air amplifiers 44, such as EXAIR Super Air Amplifiers.
- Each amplifier 44 is positioned so as to correspond with a respective opposed mold core 16 and is aligned such that a cooling fluid, i.e. ambient or chilled air, can be directed from the amplifier 44 toward the preform 12 resting on the mold core 16.
- a cooling fluid i.e. ambient or chilled air
- the number of air amplifiers 44 equals the number of molded preforms 12.
- FIG. 2 illustrates how the air amplifier 44 works in principle.
- compressed air enters into an annulus 46 where it is throttled out through a gap 48.
- the stream of air adheres to the Coanda effect as it follows the profile 50 of the outlet nozzle.
- the fast flowing air creates a pressure drop at an inlet 52 where surrounding air is sucked in, increasing the total air flow.
- EXAIR amplifiers come equipped with shims (not shown) which are used to create the previously described air jets. The thickness of a shim affects the velocity of the jets as they increase the velocity of the primary flowing air.
- the preforms 12 in a batch are first cooled using the air amplifiers 44.
- the robot 28 is rotated so that one of the sets of cooling tubes 30 or 32 is aligned with the cooled preforms 12.
- the robot 28 is then moved toward the index block 24 so that the cooled preforms 12 are ejected into the cooling tubes 30 or 32.
- the robot is then moved back away from the index block 24 and rotated so as to bring the air amplifier station 34 into position for the next cooling cycle.
- the preforms 12 After the preforms 12 have been further cooled within the cooling tubes 30 or 32, they are ejected from the cooling tubes 30 or 32. Any suitable means known in the art may be used to eject the cooled preforms 12 from the cooling tubes 30 and 32.
- air amplifiers such as the EXAIR air amplifiers
- EXAIR air amplifiers are eminently suitable for an application where a relatively small supply of high pressure air is to be used to move a large mass of surrounding air through an amplifier nozzle to perform cooling. It also has been found that the velocity and corresponding air flow rate through such an amplifier can be adjusted to provide a desired level of cooling.
- Table I shows measured cooling data achieved using the cooling system of the present invention.
- Surface temperature of the preforms 12 were measured in three regions which are shown in FIG. 3. The three regions include the gate area 60, the neck area 62, and the preform body 64.
- Each air amplifier 44 is typically closest to the gate area 60 and furthest from the neck area 62.
- Various air pressures, flow velocities (set by using different thickness shims) and distances between the air amplifier and the preform were measured and are shown in Table I.
- the neck area 62 of the preforms 12 remained enclosed by the corresponding mold inserts that are used for forming its shape. Consequently, this area of the preform is not exposed for air amplifier cooling.
- the data relating to the neck area cooling rate is presented because it was surprisingly found that there is some enhancement of the cooling rate of the neck area due to the air cooling of the adjacent body portion 64 of the preform 12.
- FIG. 4a is a graph showing a typical cooling rate (thermal decay) in the gate, neck and body portions of a preform 12 on a core without the benefit of an air amplifier.
- the characteristic rising surface temperature of the preform of about 20°C for up to 10 seconds is seen from this figure. Further, a residual surface temperature of about 90°C for the body portion 64 can be seen after 45 seconds.
- FIG. 4b is a graph showing the cooling rate which can be achieved using the cooling system of the present invention. This figure shows an improved cooling rate for the same preforms on the cores. As can be seen from the figure, the characteristic surface temperature rise is severely curtailed to less than 5°C for only 5 seconds and after 45 seconds, the surface temperature of the body portion 64 is down to approximately 45°C, which represents an almost 100% improvement.
- One of the benefits of enhanced cooling is reduced crystallinity, which is caused when the preforms' reheating is minimized.
- a second benefit from the enhanced cooling being applied directly to the preforms' outer surface is that because these surfaces harden faster this allows an earlier ejection from the cores.
- the ejection timing is typically limited by the ability of the preforms' outer surface to resist damage due to scuffing and the like, which can occur if the parts are ejected when the surface is still relatively soft.
- the enhanced air amplifier cooling reduces the time taken for the parts to reach a safe ejection temperature, thereby improving the overall molding cycle time.
- FIG. 5 the side of the clamp portion of an index style injection molding machine 10 is shown.
- three air amplifier stations 100, 104 and 106 are installed.
- the first or top station 100 is mounted on or to the top surface of the index block carriage 102.
- the station 100 can be moved toward and away from the preforms 12 by any suitable drive system (not shown) known in the art.
- the second or rear station 104 is mounted on or to the back surface of the index block carriage 102 and can be similarly moved toward and away from the preforms 12. Any suitable means (not shown) known in the art may be used to move the rear station 104 towards and away from the preforms 12.
- the third or bottom station 106 is mounted underneath the index block carriage 102 and also can be moved toward and away from the preforms 12. Again, any suitable means (not shown) known in the art may be used to move the bottom station towards and away from the preforms 12. The third station also may serve to unload the preforms 12 depositing them on conveyor 108. Any suitable means known in the art may be incorporated into the station 106 to unload the preforms 12 and deposit them onto the conveyor 108.
- each of the stations 100, 104, and 106 includes a plurality of air amplifiers 44.
- each of the stations 100, 104, and 106 has a number of air amplifiers 44 equal to the number of molded preforms being cooled.
- One set up for the configuration of FIG. 5 is to use the top station 100 to direct cooling air from the air amplifiers 44 at the gate area 60 of the preforms 12 to prevent gate crystallinity, the location where it is most prevalent.
- the preforms 12 are positioned opposite the station 100, the bulk of thermal energy in the preforms' body wall and neck areas has not migrated from mid-wall thickness to the surfaces and so a limited amount of cooling fluid is directed in these areas.
- most of the cooling air generated by the air amplifiers 44 is directed toward the body and neck areas 64 and 62 respectively, of the preforms 12 to remove the bulk of the preforms' thermal energy which has migrated to the surface by then.
- varying the amount of cooling fluid can also be employed to more efficiently use the supply.
- less air is needed for gate area cooling compared to the rear and bottom stations 104 and 106 where higher air flow rates are employed to remove the larger heat energy levels.
- FIG. 6 shows how the air flow moves over preform surfaces. Because each preform 12 is positioned on an injection mold core 16, which itself is mounted on a mold structure such as the index block 24, the air flow moving over the preform surface eventually encounters the mold surface 110 which causes the air flow to change direction. There is no provision in the mold to allow air to flow through its structure. So, with its path blocked, the air flow must change direction and move away from the preforms 12.
- the point at which the air moves away from a preform 12 is known as the separation point.
- separation points 112 are show in FIG. 6. The occurrence of a separation point 112 at some point along the preform body reduces the effectiveness of the air cooling the preform surface adjacent the neck end 62 of the preform body.
- FIG. 7 shows an alternative embodiment of a cooling system in accordance with the present invention.
- an air removal attachment 200 is mounted to the air amplifier carrier plate 42.
- the air removal attachment 200 comprises a conduit 202 connected to the carrier plate 42.
- the conduit 202 has an inlet 204 adjacent the mold surface 110.
- the conduit 202 is connected to a vacuum source 206, such as a vacuum pump, so as to vacuum air away from the mold surface 110 and thereby allow the cooling stream of air emitting from the air amplifier (s) 44 to reach further along the body of the preform 12 before separating from its surface.
- a vacuum source 206 such as a vacuum pump
- a valve 208 may be incorporated into the conduit 202 to divert some of the vacuumed air to the air amplifier (s) 44. This recirculation feature allows the air amplifier (s) 44 to optimize the supply of air.
- FIG. 8 shows yet another alternative embodiment of a cooling system in accordance with the present invention.
- each air amplifier 44 is provided with an internal bore 220 having a sufficient internal diameter to allow the air amplifier to pass over a preform 12 being cooled.
- Each air amplifier 44 is mounted on a movable plate 42' and moved over the length of the preform 12 so that its cooling air is directed onto the preform' s surface during the travel of the movable plate 42'.
- the air amplifier internal diameter to suit the various preform external diameters that may be molded, the cooling efficiency of the air stream can be fully optimized over the length of the preform surface.
- Any suitable means (not shown) known in the art may be used to move the plate 42', and hence the air amplifiers 44, from a fully retracted position A to a position B where the air amplifiers 44 are positioned over the preforms 12.
- the air amplifier cooling technique of the present invention has been disclosed using an index style injection molding machine platform, it is also feasible for the technique to be used by mounting it on a conventional robot tooling plate that removes parts from a mold and handles them for post mold cooling operations. Furthermore, the technique can be applied downstream of a robot removal device by incorporating it in downstream cooling equipment.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US397984 | 1999-09-16 | ||
US09/397,984 US6299804B1 (en) | 1999-09-16 | 1999-09-16 | Air cooling system for preform molding |
PCT/CA2000/000744 WO2001019589A1 (en) | 1999-09-16 | 2000-06-22 | Air cooling systems for preform molding |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1216134A1 true EP1216134A1 (en) | 2002-06-26 |
EP1216134B1 EP1216134B1 (en) | 2006-03-08 |
Family
ID=23573503
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00940096A Expired - Lifetime EP1216134B1 (en) | 1999-09-16 | 2000-06-22 | System and method for air cooling of preformed moldings |
Country Status (11)
Country | Link |
---|---|
US (1) | US6299804B1 (en) |
EP (1) | EP1216134B1 (en) |
JP (1) | JP3805250B2 (en) |
KR (1) | KR100445950B1 (en) |
CN (1) | CN1234519C (en) |
AT (1) | ATE319548T1 (en) |
AU (1) | AU760227B2 (en) |
BR (1) | BR0014074A (en) |
CA (1) | CA2376670C (en) |
DE (1) | DE60026524T2 (en) |
WO (1) | WO2001019589A1 (en) |
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US7632089B2 (en) * | 2004-05-07 | 2009-12-15 | Graham Packaging Pet Technologies, Inc. | Take out and cooling system and method |
US7681581B2 (en) | 2005-04-01 | 2010-03-23 | Fsi International, Inc. | Compact duct system incorporating moveable and nestable baffles for use in tools used to process microelectronic workpieces with one or more treatment fluids |
US7555926B2 (en) * | 2005-10-20 | 2009-07-07 | Ball Corporation | Temperature control mechanism for use in the manufacturing of metal containers |
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US20080178592A1 (en) * | 2007-01-25 | 2008-07-31 | Christopher Adam Bering | Pre-cleaner aspiration system |
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1999
- 1999-09-16 US US09/397,984 patent/US6299804B1/en not_active Expired - Fee Related
-
2000
- 2000-06-22 WO PCT/CA2000/000744 patent/WO2001019589A1/en active IP Right Grant
- 2000-06-22 AU AU55172/00A patent/AU760227B2/en not_active Ceased
- 2000-06-22 EP EP00940096A patent/EP1216134B1/en not_active Expired - Lifetime
- 2000-06-22 CN CNB008128839A patent/CN1234519C/en not_active Expired - Fee Related
- 2000-06-22 JP JP2001523196A patent/JP3805250B2/en not_active Expired - Fee Related
- 2000-06-22 BR BR0014074-0A patent/BR0014074A/en not_active Application Discontinuation
- 2000-06-22 KR KR10-2002-7003453A patent/KR100445950B1/en not_active IP Right Cessation
- 2000-06-22 DE DE60026524T patent/DE60026524T2/en not_active Expired - Fee Related
- 2000-06-22 CA CA002376670A patent/CA2376670C/en not_active Expired - Fee Related
- 2000-06-22 AT AT00940096T patent/ATE319548T1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO0119589A1 * |
Also Published As
Publication number | Publication date |
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ATE319548T1 (en) | 2006-03-15 |
US6299804B1 (en) | 2001-10-09 |
CN1373703A (en) | 2002-10-09 |
BR0014074A (en) | 2002-05-21 |
AU760227B2 (en) | 2003-05-08 |
KR100445950B1 (en) | 2004-08-25 |
EP1216134B1 (en) | 2006-03-08 |
JP3805250B2 (en) | 2006-08-02 |
KR20020033807A (en) | 2002-05-07 |
CA2376670C (en) | 2005-04-05 |
WO2001019589A1 (en) | 2001-03-22 |
DE60026524D1 (en) | 2006-05-04 |
CN1234519C (en) | 2006-01-04 |
CA2376670A1 (en) | 2001-03-22 |
AU5517200A (en) | 2001-04-17 |
JP2003509237A (en) | 2003-03-11 |
DE60026524T2 (en) | 2006-11-09 |
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